Manufacture of azo coloring-matter.



. addition of common salt. If, in this exthe usual manner by the action of benzoyl droxyl group, that is in position 6.

UNITED STATES PATENT onr on.

HANS BNCHERER, OF BIEBRICH, GERMANY, ASSIGNOR TO THE FIRM OF KALLE &

' COMPANY, AKTIENGESELLSCHAFT, OI BIEBRICH, GERMANY.

filed July 7, 1911.

Specification of Letters Patent.

producing a new amino-oxy-naphthalene sul-' fonic acid by subjecting the Q-amino-naphthalene-L5-disulfonic .acid to alkaline fusion. The new acid probably represents the 2-amino-5-oxy-naphthalene-Lsulfonic acid. Now I have found that, by combinin this .new acid with diazo compounds, colbring matters are obtained which are distinguished by the striking brilliancy 'of their shades beyondthat obtainable with derivatives of the 1.5-na'phthol-su1fonic acid.

The 2.5.l-amino-oxynaphthalene sulfonic acid forms two series of coloring matters accordin 'to whether its coupling is efl'ected in aci ,or alkali.

In the first case, there are apparently produced coloring matters of 2.5-am1no-naphthol the sulfonicgroup m position 1 being split off. In the alkalinecoupling a coloringmatter is formed in which the sulfonic group is retained a'ndfrom the properties of the coloring matters obtained, it is to be concluded that the azo group enters into the ortho position to the hy- The process may be illustrated by the following examples: 9.3 kilograms of anilin are diazotized inthe usual manner and run while stirring into an alkaline solution of 23.9 kilograms of the 2-amino-5 -oxynaphthalene-l-sulfonic acid. The formation of colorin matter takes place rapidly and smooth y, and a, yellow-red coloring matter is obtained which can be salted out 'by the ample the.9.3 kilograms of anilin be replaced matter which is di cultly soluble in water .para-toluidin and benzoyl-amino oxy-naph- -thalenesulfonic acid dyes cotton pure scarlet-red shades.

is obtained, which d es unmordanted cotton red-violet shades an \VhlCh, on being diazotized on the fiber, and connled with beta- I naphthol becomes blue with a tinge'of'ired: .55

If the anilin be replaced by the equivalent amount of aInin0=azo-benzene;mono-sulfonic acid,'a red coloring matter with a tinge'of blue is obtained which dyes both cottonfla'nd wool red shades with a tinge of blue and which, in aqueous solution, turns a clear blue violet when sodium carbonate is added. In an analogous manner the acid can be compounded with other diazo compounds from Patente lMay 21, 19112.

No. Drawing. Original application filed May 4, 1910. Serial No. 559,399. Divided and um application Seria1No.637,268.'

amino-azo bodies to form secondary disazo coloring matters and the like. Further -in-' vestigations have now shown that the acyl' derivatives of the new acid possess also the same remarkable property of giving, on being coupled with diazo co1npounds. co1oring .matters distinguished by the striking bril liancy of their shade. As acyl compounds may be mentioned: the urea derivative and the acetyl and benzoyl derivative of the amino-oxy-naphthalene-snlfonic acid. The

. urea derivative is produced by the action of phosgen'on an alkaline solution of the new acid. It differs fro nthe corresponding urea derivative of the 2.5.7-amino-oxy-naphthalene sulfonic acid by its marked activity of reaction toward nitrousacid in mineral acid solution (the s litting off of the area being thereby efi'ecte and the corresponding diazo compound obtained), while the urea derivative of the 2.5.7-amino-oxy-naphthalene sul fonic acid, as stated in the specification'of German Letters Patent No. 116200 is unaf fected by nitrous acid, so that, on adding small amounts of nitrite to the mineral acid solution, a powerful potassium-iodid starch reaction takes )lace. The coloring matters of the urea derlvative of the new acid differfrom the coloring matters which are produced by the coupling of the acid itself-in tingeof blue. The same applies to the-col-l' oring matters of the acetyl and benzoyhde- 71 rivative of the new amino;oxy-naphthalcne sulfonic acid. The former 18 obtained by the action of acetic anhydrid, and the latter in chlorid on the alkaline solution of the new ac1d.. The coupling 18 accomplished 1n the known manner. The coloring matter from \Yithxylidin and cumidin coloring inattors are obtainedwhich, as was to-be antler Rated, have an increased tinge of blue; a- 'S1IIl1lLI effect as regards shade is obtained with betaand, preferably, alpha-naphthylmml i i From the benzoyl-amino-Ozzy-naphthalene sulfonic acid, there are obtained according to the nature of the acid, by coupling with simple diazo compounds, only mono-azo coloring matters whereas the urea derivative" gives nno-' and dis-azo coloringjmat'ters, of which the latter are the most valuable on account of their marked affinity for cotton.

Not only can the dyestuffs above described and obtained by coupling the 2-a1nino-5- oxynaphthalene-l-sulfonic acid with diazo components be diazotized and developed either on 'or off the fibers, but also the 2- amino-5-0xynaphthalene-l-sulfonic acid can itself be diazotized and combined with suitable azo-dyestuff components.

.In the claims the term a 2-a1nino-5-oxynaphthalene-1sulfonic acid is used as generic to both the simple and the substitutedamino acids. i

What I clainris; l 1. The manufacture of am coloring matterswhich comprises diazotizing an amino compound and 'cou 'iling it with a 2-ainino-5- osynaplithalene-lsulfonic acid.

2. The mainifactureof azo coloring matters which comprises diazotizing an amino compound and coupling it with a substituted i3amino-5 oxynaphthalene-l-sulfonic acid.

3. The manufacture of azo coloring matters which comprises diazotizing an amino st-ituted in 2-positio1ron the naphthalene ring, substantially as described.

6. As new ters obtainabl e from a Q-zunino-5-oxynaphthalened-sulfonic acid and diazotized-al ins and which yield upon. reduction an ain'in and a 2-6-diamino-5-oxynaphthalene l -'sult'oni-'c' acid, substantially as described. 7. As new products the azo coloring matters, obtainable from an acyl' substituted 2- amino-5-oxynaphthalene-l-sulfonic acid and diazotized amins, andwhich yield upon reduction an ainin and an acyl-9-6-diamino-5- 'oxynaphthalene-l-sulfonic acid, substantially as described.

froducts the azocoloring mat-.-

8. As new products the axe coloring inatt'ers, obtainable from a beuzoyl substituted Q-amino-5 oxynaphthalene 1 sulfonic acid and diazotized amins, and which yield upon reduction an amin and a benzoyl-Q-(i-diamino-5-oxynaphthalene-l-sulfonic acid, substantially as described.

9. As a new product the azo coloring mat.- ter. obtainable from diazotized cuinidin and the henzoyl-deriyative of the Q-amino-S-oxynaphthalenel-sulfonic acid. constituting in dry state a brownish-redpowder, soluble in hot water with a red color and giving a solution which in a hot condition not precipitated-by diluted acetic acid. whereas by the addition of diluted hydrochloric or sulfuric acid the dyestufi is separated in form of brownish flakes soluble in conccnt ated sulfuric acid with a yiolet-red color from-which solution brownish-red flakes are separated by the addition of water; being decomposed by Zinc dust in. neutral solution into cumidin and -benzoyl diamino-oxynaphthalene sulfonic acid; which latter turns blue by the oxidizing action of the air in the presence of alkali and furnishes a greenish blue precipitate by the addition of ferro-chlorid; and dyeing vegetable fibers beautiful scarlet red shades.

In testimony whereof I have signed my name to this specification in the presence of two subscribing witnesses.

HANS BUCHE ER Witnesses:

MARIA Mnnnn, HERMAN PLISCHER. 

